WO2015045918A1 - Composition adhésive autocollante thermoconductrice, article stratiforme adhésif autocollant thermoconducteur, leur procédé de production et matériel électronique - Google Patents

Composition adhésive autocollante thermoconductrice, article stratiforme adhésif autocollant thermoconducteur, leur procédé de production et matériel électronique Download PDF

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WO2015045918A1
WO2015045918A1 PCT/JP2014/074263 JP2014074263W WO2015045918A1 WO 2015045918 A1 WO2015045918 A1 WO 2015045918A1 JP 2014074263 W JP2014074263 W JP 2014074263W WO 2015045918 A1 WO2015045918 A1 WO 2015045918A1
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meth
sensitive adhesive
conductive pressure
heat conductive
parts
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PCT/JP2014/074263
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Japanese (ja)
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明子 北川
拓朗 熊本
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日本ゼオン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/64—Heat extraction or cooling elements
    • H01L33/641—Heat extraction or cooling elements characterized by the materials

Definitions

  • the present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet.
  • the present invention relates to an electronic device including a shaped molded body.
  • thermo conductive pressure-sensitive adhesive composition a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • sheet a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • thermo conductive pressure-sensitive adhesive sheet a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • thermoally conductive pressure-sensitive adhesive sheet-like molded product a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are mainly intended to transfer heat from the heat generating body to the heat radiating body, and therefore it is preferable to improve the heat conductivity. .
  • various fillers For example, Patent Document 1 discloses a technique of adding a filler such as alumina or aluminum hydroxide to an acrylic heat conductive material.
  • the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded article becomes brittle and the tensile strength may be lowered.
  • this invention makes it a subject to provide a heat conductive pressure-sensitive-adhesive composition and a heat conductive pressure-sensitive-adhesive sheet-like molded object with high tensile strength, even if the addition amount of the filler which improves heat conductivity is increased. Moreover, these manufacturing methods and the electronic device provided with this heat conductive pressure-sensitive-adhesive composition or this heat conductive pressure-sensitive-adhesive sheet-like molded object are provided.
  • (meth) acryl means “acryl and / or methacryl”.
  • the “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. It means a filler whose own thermal conductivity is 0.3 W / m ⁇ K or more.
  • the “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction for obtaining a polymer containing a structural unit derived from (meth) acrylate monomer ( ⁇ 1).
  • 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) Producing a mixed composition comprising 250 parts by mass or more and 1300 parts by mass or less of the thermally conductive filler (B) and 0.05 part by mass or more and 6 parts by mass or less of the silane coupling agent (C);
  • a method for producing a heat conductive pressure-sensitive adhesive composition (F) comprising a step of performing a polymerization reaction of at least a (meth) acrylic acid ester monomer ( ⁇ 1).
  • 4th aspect of this invention is (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) containing (meth) acrylic resin composition (A) 100 mass parts.
  • Producing a mixed composition comprising 250 parts by mass or more and 1300 parts by mass or less of the thermally conductive filler (B) and 0.05 part by mass or more and 6 parts by mass or less of the silane coupling agent (C);
  • a heating element and the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the heating element, or the heating element and the heating element. It is the electronic device provided with the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of the 2nd aspect of the said this invention bonded.
  • a heat conductive pressure-sensitive adhesive composition and a heat conductive pressure-sensitive adhesive sheet-like molded article having high tensile strength can be obtained even if the amount of filler added to improve the heat conductivity is increased.
  • thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) it is considered to increase the amount of the thermally conductive filler (B) added. It is done. However, if a large amount of the heat conductive filler (B) is added, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) may become brittle and the tensile strength may be reduced. was there.
  • the present inventors blended a predetermined amount of the silane coupling agent (C) into the (meth) acrylic resin composition (A), so that the thermal conductivity feeling can be increased even if the amount of the thermally conductive filler (B) is increased to some extent. It has been found that the tensile strength of the pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is difficult to decrease.
  • the heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition (A) containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
  • the thermally conductive filler (B), and the silane coupling agent (C) at least a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) is performed. It will be.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is at least (meth) acryl after shape
  • the polymerization reaction of the acid ester monomer ( ⁇ 1) is performed.
  • the materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.
  • the (meth) acrylic resin composition (A) used in the present invention contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1). May contain a functional monomer.
  • the polymerization reaction of at least (meth) acrylic acid ester monomer ((alpha) 1) is carried out. Done.
  • the polymer containing the structural unit derived from the (meth) acrylate monomer ( ⁇ 1) is mixed and / or partially bonded to the component of the (meth) acrylate polymer (A1). .
  • the proportion of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1) used is (mass) acrylic resin composition (A) being 100% by mass
  • the (meth) acrylate polymer (A1) is preferably 5% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 75% by mass or more and 95% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 7% by mass or more and 15% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 80% by mass or more and 92.5% by mass or less.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are formed. It becomes easy to do.
  • the (meth) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the unit (a1) and the monomer unit (a2) having an organic acid group.
  • the (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer is not particularly limited.
  • ethyl acrylate the glass transition temperature of the homopolymer is -24 ° C
  • n-propyl acrylate (-37 ° C)
  • n-butyl acrylate (-54 ° C)
  • sec-butyl acrylate (-22 ° C)
  • n-octyl acrylate -65 ° C
  • 2-ethylhexyl acrylate -50 ° C
  • n-octyl methacrylate (-25 ° C)
  • a (meth) acrylic acid alkyl ester that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C.
  • n-decyl methacrylate (-49 ° C.); 2-methoxyethyl acrylate
  • the glass transition temperature is ⁇ 50 ° C.), 3-methoxypropyl acrylate (-75 ° C.), 3-methoxybutyl acrylate (-56 ° C.), ethoxymethyl acrylate ( ⁇ 50 ° C.), etc.
  • (meth) acrylic acid alkoxyalkyl esters that form a homopolymer of 20 ° C. or lower. Among them, (meth) acrylic acid alkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C.
  • (meth) acrylic acid alkoxyalkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower (meth) acrylic acid alkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is more preferable, and 2-ethylhexyl acrylate is more preferable.
  • acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
  • the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1).
  • it is used for polymerization in such an amount that it is more preferably 85% by mass or more and 99.5% by mass or less.
  • the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.
  • the monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group.
  • monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
  • the monomer having a carboxyl group include, for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and ⁇ , ⁇ such as itaconic acid, maleic acid, and fumaric acid.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified.
  • the monomer having a sulfonic acid group examples include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
  • the monomer (a2m) among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is more preferable. (Meth) acrylic acid is particularly preferred. These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.
  • the monomer unit (a2) derived from the monomer unit (a2) is preferably 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1). More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass.
  • the usage-amount of the monomer (a2m) which has an organic acid group exists in the said range, it will become easy to maintain the viscosity of the polymerization system at the time of superposition
  • the monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) by polymerization of the monomer (a2m) having an organic acid group as described above.
  • an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is formed.
  • the (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group.
  • the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.
  • Examples of the monomer having an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
  • Examples of monomers having an amide group include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
  • the monomer (a3m) having a functional group other than the organic acid group one type may be used alone, or two or more types may be used in combination.
  • the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount.
  • the monomer (a3m) of 10% by mass or less it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.
  • the (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer may be contained.
  • the monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), ⁇ , ⁇ -ethylenic monomers. Saturated polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer and the like can be mentioned.
  • the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
  • alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyltoluene and the like.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
  • olefin monomer examples include ethylene, propylene, butene, pentene and the like.
  • the monomer (a4m) one type may be used alone, or two or more types may be used in combination.
  • the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.
  • the (meth) acrylic acid ester polymer (A1) has the above-mentioned (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • Monomer (a2m) a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
  • the polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. .
  • solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable.
  • the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.
  • the method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
  • the thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
  • Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
  • the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited.
  • the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and may be in the range of 1,000 to 1,000,000 in terms of standard polystyrene. Preferably, it is in the range of 100,000 or more and 500,000 or less.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
  • the (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains the (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
  • a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
  • a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer ( ⁇ 1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the (meth) acrylic acid ester monomer ( ⁇ 1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.
  • Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to.
  • a monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 30% by mass or less, and more preferably 10% by mass or less.
  • the (meth) acrylic acid ester monomer ( ⁇ 1) in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.
  • Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m).
  • the body can be mentioned.
  • a monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • a polyfunctional monomer in the present invention, can also be used in the (meth) acrylic resin composition (A). Usually, at the time of polymerization such as radical thermal polymerization, a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer. However, a polyfunctional monomer may be used in order to form a desired amount of a crosslinked structure more reliably.
  • the polyfunctional monomer that can be used in the present invention one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer ( ⁇ 1) is used.
  • the polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal.
  • intramolecular and / or intermolecular crosslinking can be introduced into the copolymer to increase the cohesive force as a pressure-sensitive adhesive.
  • polyfunctional monomer examples include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro Other substituted triazines, such as chill)
  • monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used.
  • polyfunctional (meth) acrylate is preferable, and pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are more preferable.
  • a polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polyfunctional monomer used is preferably 10% by mass or less, based on the (meth) acrylic resin composition (A) as 100% by mass, and is 0.5% by mass or more and 5% by mass or less. Is more preferable.
  • ⁇ Polymerization initiator> When obtaining the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G), the components contained in the (meth) acrylic resin composition (A) are polymerized as described above. . In order to accelerate the polymerization reaction, it is preferable to use a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator.
  • an organic peroxide thermal polymerization initiator is used. Is preferably used.
  • acylphosphine oxide compounds are preferred.
  • Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • azo-based thermal polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
  • organic peroxide thermal polymerization initiator examples include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • organic peroxide thermal polymerization initiators those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.
  • the amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). More preferably, it is 0.3 to 2 parts by mass.
  • the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface. Moreover, by making the usage-amount of a polymerization initiator into the said range, superposition
  • the heat conductive filler (B) the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be improved by adding, A filler having its own thermal conductivity of 0.3 W / m ⁇ K or more can be used.
  • thermally conductive filler (B) examples include aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and other metal hydroxides; aluminum oxide ( Alumina), metal oxides such as magnesium oxide and zinc oxide; metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate water Examples thereof include: Japanese; Dosonite; Silica; Expanded graphite powder, artificial graphite, carbon black, carbon fiber, and other carbon-containing conductive fillers. Of these, metal hydroxides and metal oxides are preferable, and aluminum hydroxide and aluminum oxide (alumina) are more preferable.
  • a heat conductive filler (B) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the heat conductive filler (B) contained in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition.
  • (A) It is 250 mass parts or more and 1300 mass parts or less with respect to 100 mass parts, it is preferable that they are 400 mass parts or more and 1200 mass parts or less, and it is more preferable that they are 400 mass parts or more and 800 mass parts or less.
  • Mixing which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B) to the upper limit or less.
  • the average particle size of the heat conductive filler (B) is preferably 0.5 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.8 ⁇ m or more and 12 ⁇ m or less.
  • the BET specific surface area of the thermally conductive filler (B) is preferably 0.3 m 2 / g or more and 10 m 2 / g or less, and more preferably 0.5 m 2 / g or more and 5 m 2 / g or less. preferable.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are less likely to become brittle and further suppress the decrease in tensile strength. it can.
  • the “average particle diameter” means that measured by the method described below. That is, a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used, and measurement is performed by a microsorting control method (a method in which the measurement target particles are allowed to pass only in the measurement region and the measurement reliability is improved). According to this measurement method, when the measurement target particles 0.01 g to 0.02 g are flowed into the cell, the measurement target particles flowing in the measurement region are irradiated with the semiconductor laser light having a wavelength of 670 nm. By measuring the scattering and diffraction of laser light with a measuring instrument, the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
  • the “BET specific surface area” means that measured by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen gas to the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of the gas before and after passing through the sample cell changes during the adsorption and desorption of nitrogen gas, this change is detected by a thermal conductivity detector (TCD) using a gas with a constant mixing ratio of nitrogen and helium as a control.
  • TCD thermal conductivity detector
  • the adsorption amount and desorption amount of nitrogen gas are obtained.
  • a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample.
  • the BET specific surface area can be determined by dividing the determined surface area by the mass of the sample.
  • silane coupling agent (C) ⁇ Silane coupling agent (C)> Next, the silane coupling agent (C) will be described. As in Examples described later, the silane coupling agent (C) is mixed with the (meth) acrylic resin composition (A) described above together with the thermally conductive filler (B) to produce a mixed composition, A conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) are obtained. Thus, a heat conductive filler (B) is made to contain a silane coupling agent (C) in a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G).
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet form can be easily adapted to the (meth) acrylic resin composition (A). It can suppress that a molded object (G) becomes difficult to become weak and a tensile strength falls.
  • silane coupling agent (C) a known silane coupling agent can be used. Specific examples include silane coupling agents in which a vinyl group is directly bonded to a silicon atom, such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy group-containing silane coupling agents such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc.
  • silane coupling agents in which a vinyl group is directly bonded to a silicon atom such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane
  • Silane coupling agent having an aromatic ring and a vinyl group bonded thereto; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy (Meth) acryloxy group-containing silane coupling agents such as propyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl -N- (1,3-dimethyl-
  • amino group-containing silane coupling agents and salts thereof 3 Ureido group-containing silane coupling agents such as ureidopropyltriethoxysilane; halogen atom-containing silane coupling agents such as 3-chloropropyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, And sulfur atom-containing silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide; and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.
  • a (meth) acryloxy group-containing silane coupling agent is preferable, and 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane are more preferable.
  • the amount of the silane coupling agent (C) contained in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is the (meth) acrylic resin composition (A). It is 0.05 mass part or more and 6 mass parts or less with respect to 100 mass parts, it is preferable that they are 0.3 mass part or more and 5 mass parts or less, and it is 0.5 mass part or more and 4 mass parts or less. More preferred. Mixing which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the silane coupling agent (C) to the upper limit or less.
  • the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive are obtained by containing the thermally conductive filler (B). It becomes easy to suppress that the tensile strength of an adhesive sheet-like molded object (G) falls.
  • phosphate ester for the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded product (G) of the present invention.
  • phosphate ester it becomes easy to give the flame retardance excellent in the heat conductive pressure-sensitive-adhesive composition (F) and the heat conductive pressure-sensitive-adhesive sheet-like molded object (G).
  • the phosphate ester used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • the viscosity of the phosphate ester is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
  • a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
  • (1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
  • (2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
  • the container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the condensed phosphate ester in the container.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa ⁇ s].
  • the coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
  • the phosphate ester used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester is liquid when mixed, the workability is good, and it is easy to form the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G). become.
  • the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less.
  • the glass transition temperature of the (meth) acrylic resin composition (A) is set to be equal to or higher than the volatilization or polymerization of monomers contained in the (meth) acrylic resin composition (A). Since it becomes easy to prevent the reaction from starting, the environmental performance and workability can be improved.
  • a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester.
  • condensed phosphate ester means one having a plurality of phosphate ester moieties in one molecule
  • non-condensed phosphate ester means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of phosphate esters that satisfy the conditions described so far are listed below.
  • condensed phosphate ester examples include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
  • aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyal
  • non-condensed phosphate ester examples include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris ( ⁇ -chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
  • Phosphoric acid ester may be used alone or in combination of two or more.
  • the amount thereof is (meth) acrylic resin composition (A ) Is 100 parts by mass, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 30 parts by mass or more and 70 parts by mass or less.
  • the heat conductive filler (B) is added to the (meth) acrylic resin composition (A).
  • a silane coupling agent (C) in a predetermined amount the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet can be used even if the amount of the heat conductive filler (B) added is increased to some extent. It can suppress that a shaped molded object (G) becomes weak. Therefore, according to the present invention, it is possible to obtain a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) having high tensile strength and high thermal conductivity. .
  • the thermally conductive pressure-sensitive adhesive composition (F) and thermally conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention include, in addition to the materials described above, the above-described thermally conductive pressure-sensitive adhesive of the present invention.
  • Various known additives can be added within a range in which the performance of the adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be satisfied.
  • foaming agents include foaming aids; flame retardant thermally conductive inorganic compounds such as metal hydroxides and metal salt hydrates other than the above-described thermally conductive filler (B); glass Fiber: Thermally conductive inorganic compound other than the above-mentioned thermally conductive filler (B), such as expanded graphite powder and PITCH-based carbon fiber; External cross-linking agent; Pigment such as carbon black and titanium dioxide; Other filler such as clay Nanoparticle such as fullerene and carbon nanotube; antioxidant such as polyphenol, hydroquinone and hindered amine; thickener such as acrylic polymer particles, fine silica and magnesium oxide;
  • foaming agents including foaming aids
  • flame retardant thermally conductive inorganic compounds such as metal hydroxides and metal salt hydrates other than the above-described thermally conductive filler (B)
  • glass Fiber Thermally conductive inorganic compound other than the above-mentioned thermally conductive filler (B), such as expanded graphite powder and
  • the heat conductive pressure-sensitive adhesive composition (F) is prepared by mixing the substances described so far to prepare a mixed composition, and then, in the mixed composition, at least a (meth) acrylic acid ester monomer ( ⁇ 1) It can be obtained by conducting a polymerization reaction.
  • the manufacturing method of the heat conductive pressure-sensitive adhesive composition (F) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
  • a step of producing a mixed composition comprising an acrylic resin composition (A), a thermally conductive filler (B), and a silane coupling agent (C), and at least (meth) acrylic in the mixed composition
  • Other substances that can be used and preferable content ratios of the respective substances are as described above, and a detailed description thereof is omitted here.
  • the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and molding the mixed composition into a sheet shape, or It can be obtained by performing at least a (meth) acrylate monomer ( ⁇ 1) polymerization reaction while forming the mixed composition into a sheet.
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1)
  • a step of producing a mixed composition comprising a (meth) acrylic resin composition (A), a thermally conductive filler (B), and a silane coupling agent (C); and molding the mixed composition into a sheet shape
  • the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention it is preferable to heat the polymerization reaction.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylate monomer ( ⁇ 1) proceeds.
  • the temperature range varies depending on the type of polymerization initiator used, but is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 120 ° C. or higher and 180 ° C. or lower.
  • the method for molding the mixed composition into a sheet shape is not particularly limited. Suitable methods include, for example, a method of forming a sheet by applying the mixed composition on a process paper such as a release-treated polyester film, and the mixing between two release-processed papers. A method of forming a sheet by pressing between the rolls sandwiching the composition, and a method of forming the sheet by extruding the mixed composition using an extruder and controlling the thickness through a die at that time Etc.
  • the process paper is not particularly limited, for example, a release-treated polyethylene terephthalate film or a release-treated polyethylene naphthalate film can be used. Among these, a polyethylene terephthalate film subjected to a release treatment is preferable.
  • the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) can be set to, for example, 0.05 mm or more and 5 mm or less. By reducing the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded article (G), the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded article (G) can be reduced. From this viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 2 mm. On the other hand, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) is preferably 0.1 mm.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate.
  • the material which comprises the said base material is not specifically limited.
  • Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone.
  • Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
  • a heat-resistant polymer film can be used.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention have high heat conductivity and pressure-sensitive adhesiveness, By interposing between a heat generating body and a heat radiating body, it can be used for applications such as efficiently conducting heat conduction from the heat generating body to the heat radiating body.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention are attached to an electronic component which is a heating element provided in an electronic device, and the electronic component Can be used as part.
  • FIG. 1 is a diagram for explaining an example of use of a heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • FIG. 1A is a perspective view schematically showing a part of an electronic device such as a personal computer.
  • FIG. 1A shows a substrate 1, an electronic component 2 that is a heating element installed on the substrate 1, a heat sink 3 that is a radiator, and a thermally conductive pressure-sensitive adhesive disposed between the electronic component 2 and the heat sink 3.
  • the sheet-like molded article (G) 4 is shown.
  • a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 4 is sandwiched and fixed between the electronic component 2 and the heat sink 3, thereby forming a heat conductive pressure-sensitive adhesive sheet-like mold.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) 4 is bonded to the electronic component 2 and the heat sink 3. And since the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 4 has high heat conductivity, the heat
  • FIG. 1B schematically shows a state in which the NPN transistor 12a and the PNP transistor 12b, which are heating elements, are attached to the heat sink 13, which is a radiator, through the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14, 14.
  • FIG. 1B by attaching the NPN transistor 12a and the PNP transistor 12b to the heat sink 13 via the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14 and 14, the heat conductive feeling is obtained.
  • one heat conductive pressure-sensitive adhesive sheet-like molded body (G) 14 is bonded to the NPN transistor 12a and the heat sink 13, and the other heat
  • the conductive pressure-sensitive adhesive sheet-like molded body (G) 14 is bonded to the PNP transistor 12 b and the heat sink 13.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 14 has high heat conductivity, the heat
  • both the NPN transistor 12a and the PNP transistor 12b are attached to one heat sink 13 via the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14 and 14 having high heat conductivity.
  • the temperature difference between the NPN transistor 12a and the PNP transistor 12b can be suppressed.
  • FIG. 1C is a cross-sectional view schematically showing a state in which two transistors 22 and 22 that are heating elements are fixed via a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 24.
  • two heat generating elements 22 and 22 are fixed via a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 24, thereby forming a heat conductive pressure-sensitive adhesive sheet. Due to the pressure-sensitive adhesive property of the molded body (G) 24, the thermally conductive pressure-sensitive adhesive sheet-shaped molded body (G) 24 is bonded to the two heating elements 22 and 22.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 24 has high heat conductivity, if one temperature of two heat generating bodies 22 and 22 becomes high compared with the other, from one side. Since heat can be quickly transmitted to the other side, it is possible to suppress the occurrence of a temperature difference between the two heating elements 22 and 22.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) was used in the example shown in FIG. 1, it replaces with a heat conductive pressure-sensitive-adhesive sheet-like molded object (G), and a heat conductive pressure-sensitive-adhesive composition.
  • a thing (F) can also be used similarly.
  • the heat sink is used as the heat radiating body.
  • a housing of an electronic component or the like can be used as the heat radiating body.
  • other usage examples of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention will be described.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention can be used as a part of an electronic component provided in an electronic device.
  • the electronic device and electronic component include electroluminescence (EL), a component around a heat generating part in a device having a light emitting diode (LED) light source, a component around a power device such as an automobile, a fuel cell, a solar cell, and a battery.
  • EL electroluminescence
  • LED light emitting diode
  • Devices and parts having heat generating parts such as mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystal panels, surface conduction electron-emitting device displays (SED), plasma display panels (PDP), or integrated circuits (ICs) Can be mentioned.
  • PDAs personal digital assistants
  • SED surface conduction electron-emitting device displays
  • PDP plasma display panels
  • ICs integrated circuits
  • an LED light source is exemplified below. Examples of usage can be mentioned.
  • LED light source is directly attached to the LED light source; sandwiched between the LED light source and a heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); , Heat pipe, graphite sheet, etc.); used as a housing surrounding the LED light source; pasted on a housing surrounding the LED light source; filling a gap between the LED light source and the housing;
  • heat dissipation material heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.
  • Examples of LED light source applications include backlight devices for display devices having transmissive liquid crystal panels (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; Lighting; and the like.
  • LED light source examples include the following. That is, PDP panel; IC heating part; Cold cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High luminance light emitting LED light source; High luminance light emitting organic EL light source; And so on.
  • examples of the method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention include affixing to the housing of the apparatus.
  • affixing to the housing of the apparatus.
  • a device provided in an automobile or the like it is affixed inside a casing provided in the automobile; affixed outside the casing provided in the automobile; a heat generating part (inside the casing provided in the automobile) Connecting the car navigation / fuel cell / heat exchanger) and the housing; affixing to a heat sink connected to the heat generating part (car navigation / fuel cell / heat exchanger) in the housing of the automobile; Etc.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention can be used in the same manner.
  • personal computers homes; TVs; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Organic EL display; laptop computer; PDA; fuel cell; semiconductor device; rice cooker; washing machine; laundry dryer; optical semiconductor device combining optical semiconductor elements and phosphors; Is mentioned.
  • the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) of the invention are not limited to the above-described usage methods, and may be used in other methods depending on the application. Is possible. For example, used for heat uniformity of carpets and warm mats, etc .; used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer,
  • a heat conductive pressure-sensitive adhesive sheet-like molded body sandwiched between two release PET films was prepared, and a test piece was prepared by cutting it into a size of 50 mm ⁇ 110 mm. Thereafter, the release PET film was peeled off from one surface of the test piece, and a wrap film (made of polyvinyl chloride, thickness 8 ⁇ m) was pasted on the surface from which the release PET film was peeled off so as not to enter air. .
  • the size of the wrap film may be larger than the adhesive surface of the test piece.
  • the thermal conductivity was measured by the method.
  • the thermal conductivity [W / m ⁇ K] was measured by a non-stationary hot wire comparison method using a rapid thermal conductivity meter (QTM-500, manufactured by Kyoto Electronics Industry Co., Ltd.).
  • QTM-500 rapid thermal conductivity meter
  • silicone sponge current value: 1A
  • silicone rubber current value: 2A
  • quartz current value: 4A
  • Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • a thermostatic bath manufactured by Toki Sangyo Co., Ltd., Viscomate 150III
  • a Hobart mixer manufactured by Kodaira Manufacturing Co., Ltd., ACM-5LVT type, capacity: 5 L
  • the temperature control of the Hobart container was set to 40 ° C.
  • the rotation speed scale was set to 3
  • the mixture was stirred for 10 minutes. This process is referred to as a first mixing process.
  • silane coupling agent (C) manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103, 3-acryloxypropyltrimethoxysilane
  • phosphate ester manufactured by Ajinomoto Fine Techno Co., Ltd., Leofos 65
  • 50 parts by weight of the compound: triaryl isopropylated compound, and aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd., BF-083, average particle size: 8 ⁇ m, BET specific surface area: 0.001.
  • the mixed composition obtained through the first mixing step and the second mixing step is hung on a release PET film having a thickness of 75 ⁇ m, and another release agent having a thickness of 75 ⁇ m is further applied on the mixed composition. Covered with PET film.
  • This laminate in which the mixed composition was sandwiched between the release PET films was passed between two rolls adjusted to a distance of 650 ⁇ m to form the mixed composition into a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes.
  • the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized, and at the same time, the polyfunctional monomer as a crosslinking agent allows the (meth) acrylic acid ester polymer ( A1-1) and a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer are crosslinked to form a thermally conductive pressure-sensitive adhesive sheet-like molded product (hereinafter simply referred to as “sheet”) (G1). )
  • sheet thermally conductive pressure-sensitive adhesive sheet-like molded product
  • the polymerization conversion rate of all monomers was calculated from the amount of residual monomers in the sheet (G1) and found to be 99.9%.
  • Example 2 to 8 and Comparative Examples 1 to 3 Sheets (G2 to G8) according to Examples 2 to 8 and sheets according to Comparative Examples 1 to 3 in the same manner as Example 1 except that the composition of each substance was changed as shown in Tables 2 and 3 GC1 to GC3) were produced.
  • Tables 2 and 3 show the amount of each substance in parts by mass.
  • Example 2 instead of “KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd. as the silane coupling agent (C), “KBM-503” (3-methacryloxypropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.) was used. Silane) was used.
  • Example 7 alumina (Showa Denko Co., Ltd., AL-47-H, average particle size: 1.1 ⁇ m, BET specific surface area: 2 m 2 / g) was used as the thermally conductive filler (B) in the second mixing step. Also used. Moreover, in the comparative example 2, it replaced with the silane coupling agent (C), and used the titanate coupling agent (Ajinomoto Finetech Co., Ltd. product, Preneact TTS, isopropyl triisostearoyl titanate). Further, in Comparative Example 3, a hydroxyl group-terminated liquid polyolefin (Idol Sangyo Co., Ltd., Epaul) was used in place of the (meth) acrylic resin composition.
  • a hydroxyl group-terminated liquid polyolefin Idol Sangyo Co., Ltd., Epaul
  • the sheets (G1 to G8) according to the examples all had high tensile strength even when a large amount of thermally conductive filler (aluminum hydroxide, alumina) was added. Therefore, thermal conductivity and tensile strength were high.
  • seat (GC1 and GC2) concerning the comparative examples 1 and 2 which did not use a silane coupling agent had low tensile strength.
  • seat (GC3) concerning the comparative example 3 which replaced with the (meth) acrylic acid ester polymer and used the hydroxyl-terminated liquid polyolefin used the silane coupling agent, its tensile strength was low.

Abstract

Selon l'invention, une réaction de polymérisation d'au moins un monomère ester (méth)acrylique (α1) est effectuée dans une composition mélangée qui comprend 100 parties en masse d'une composition de résine (méth)acrylique (A) qui comprend un polymère d'ester (méth)acrylique (A1) et le monomère ester (méth)acrylique (α1), 250 à 1300 parties en masse d'une charge thermoconductrice (B) et 0,05 à 6 parties en masse d'un agent de couplage silane (C). De cette manière, on produit une composition adhésive autocollante thermoconductrice et un article stratiforme adhésif autocollant thermoconducteur qui ont une excellente souplesse et un bon aspect externe tout en ayant une quantité accrue d'un additif qui améliore la conductivité thermique.
PCT/JP2014/074263 2013-09-26 2014-09-12 Composition adhésive autocollante thermoconductrice, article stratiforme adhésif autocollant thermoconducteur, leur procédé de production et matériel électronique WO2015045918A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004339426A (ja) * 2003-05-19 2004-12-02 Nippon Shokubai Co Ltd 放熱材料用樹脂組成物
JP2009235146A (ja) * 2008-03-26 2009-10-15 Achilles Corp アクリル系樹脂シート状成形体
JP2010106244A (ja) * 2008-09-30 2010-05-13 Sony Chemical & Information Device Corp アクリル系絶縁性接着剤
WO2013047145A1 (fr) * 2011-09-28 2013-04-04 日本ゼオン株式会社 Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique
WO2013061830A1 (fr) * 2011-10-28 2013-05-02 日本ゼオン株式会社 Composition auto-adhésive thermiquement conductrice, corps moulé en forme de feuilles auto-adhésif thermiquement conducteur, procédé de fabrication associé et composant électronique
WO2013084750A1 (fr) * 2011-12-06 2013-06-13 日本ゼオン株式会社 Composition d'agent adhésif autocollant thermoconducteur, moulage en forme de feuille d'adhésif autocollant thermoconducteur, procédés de production correspondants et dispositif électronique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004339426A (ja) * 2003-05-19 2004-12-02 Nippon Shokubai Co Ltd 放熱材料用樹脂組成物
JP2009235146A (ja) * 2008-03-26 2009-10-15 Achilles Corp アクリル系樹脂シート状成形体
JP2010106244A (ja) * 2008-09-30 2010-05-13 Sony Chemical & Information Device Corp アクリル系絶縁性接着剤
WO2013047145A1 (fr) * 2011-09-28 2013-04-04 日本ゼオン株式会社 Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique
WO2013061830A1 (fr) * 2011-10-28 2013-05-02 日本ゼオン株式会社 Composition auto-adhésive thermiquement conductrice, corps moulé en forme de feuilles auto-adhésif thermiquement conducteur, procédé de fabrication associé et composant électronique
WO2013084750A1 (fr) * 2011-12-06 2013-06-13 日本ゼオン株式会社 Composition d'agent adhésif autocollant thermoconducteur, moulage en forme de feuille d'adhésif autocollant thermoconducteur, procédés de production correspondants et dispositif électronique

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